论文标题
电沉积氧化锰的循环伏安法期间的可逆和不可逆过程作为氧气进化反应的催化剂
Reversible and irreversible processes during cyclic voltammetry of an electrodeposited manganese oxide as catalyst for the oxygen evolution reaction
论文作者
论文摘要
多年来,由于其低毒性,高丰度和富含氧化还原化学的氧化物反应(OER),多年来,锰氧化物在广泛的电催化剂中引起了很多关注。尽管许多以前的研究都集中在这些材料的活性上,但从科学的角度和应用中,对与激活或降解有关的材料转换具有更好的理解。我们在MN-K和MN-L边缘处通过循环伏安法,扫描电子显微镜和X射线吸收光谱来研究含NA的MNOX,没有碱性溶液中的NA含量。原始薄膜被分配给分层边缘共享的MN3+/4+氧化物,其Mn-O键长的长度主要为1.87Å,其中一些为2.30Å,而Mn-Mn键长为2.87Å,基于与扩展的X射线优质结构的拟合。 OER发作前电压下的电流降低遵循了功率定律,该法律具有三种不同的指数,具体取决于周期的数量,塔菲尔斜率从186 \ pm 48 \ pm 48 \ pm 18 mv dec-1后100个循环后降低,这是我们根据未造成的中间中间人的表面覆盖率来解释的。 MN-K边缘处的验尸显微镜和散装光谱没有显示显微结构,大量局部结构或大量MN价的变化。然而,MNOX的表面区域被氧化朝Mn4+氧化,这解释了与文献一致的电流的还原。令人惊讶的是,我们发现在开路(OC)30分钟后,MNOX在其中电流以及塔菲尔斜率增加。 OC期间的重新激活过程至关重要,因为将电催化剂耦合到间歇性功率来源(例如用于可持续能源生产的太阳能)时,OC是不可避免的。
Manganese oxides have received much attention over the years among the wide range of electrocatalysts for the oxygen evolution reaction (OER) due to their low toxicity, high abundance and rich redox chemistry. While many previous studies focused on the activity of these materials, a better understanding of the material transformations relating to activation or degradation is highly desirable, both from a scientific perspective and for applications. We electrodeposited Na-containing MnOx without long-range order from an alkaline solution to investigate these aspects by cyclic voltammetry, scanning electron microscopy and x-ray absorption spectroscopy at the Mn-K and Mn-L edges. The pristine film was assigned to a layered edge-sharing Mn3+/4+ oxide with Mn-O bond lengths of mainly 1.87 Å and some at 2.30 Å as well as Mn-Mn bond lengths of 2.87 Å based on fits to the extended x-ray fine structure. The decrease of the currents at voltages before the onset of the OER followed power laws with three different exponents depending on the number of cycles and the Tafel slope decreases from 186 \pm 48 to 114 \pm 18 mV dec-1 after 100 cycles, which we interpret in the context of surface coverage with unreacted intermediates. Post-mortem microscopy and bulk spectroscopy at the Mn-K edge showed no change of the microstructure, bulk local structure or bulk Mn valence. Yet, the surface region of MnOx oxidized toward Mn4+, which explains the reduction of the currents in agreement with literature. Surprisingly, we find that MnOx reactivates after 30 min at open-circuit (OC), where the currents and also the Tafel slope increase. Reactivation processes during OC are crucial because OC is unavoidable when coupling the electrocatalysts to intermittent power sources such as solar energy for sustainable energy production.